electzodes immersed in inc sulfate solutions at diferent concentrations: Zo(s\izn?=(0.1MYIIZ0™*(1.OMZn(5) (2.42) Another example ofa concentration cellistwo standard hydrogen electrodes immersed into two HCI solutions of different concentrations: Pe(s)Ha(g, Latm)/HCl(@)/1 HCH )Fa(g, LatmyP(s) (2.43) In the above cel, HCl is in two different concentrations. The activity (molality > activity coefficient) a is greater than activity a a >a. Several types of concentration cells are enco tered in corrosion. For example, a concentration cellis formed if one end of a pipe is exposed to soil and the other end to air. The end of the pipe in air is exposed to a high concentration of omygen than the end ofthe pipe in the soil. The formation of a concentration cell leads to differential aeration corrosion in buried structures in the soil 2.9 Liquip JUNCTION POTENTIAL Foraccurate measurement of emf, two conditions aust be saisied: (a) The cell reaction must be reversible and (b) no current must be drawn from the cell ‘The boundary between two electrolytic solu- tions with different concentrations is a source cof irreversibility in measuring the emf of the cells. ‘The potential difference developed at the boundary is called ‘Liquid Junction Potential” ‘The potential difference is caused by the rigration of ions from one eletrolyce to another electrolyte, Let us take the ease of concentrated: HCI forming a junction with dilute HCL Both HY and CI” ione diffuse from concentrated HCL to dilute ICL, The bydrogen ion moves faster and, therefore, the dilute solution becomes posi- tively charged due to ingress of H* ions from the stronger acid solution and the more concentrated Basic conceptsin corrosion 23 solution thus acquites a relative negative charge The consequent potential difference across the double layer, which isa positively charged layer in the dilute solution side and a negatively charged yer in the concentrated solution, may effect the tem ofthe cell seriously in certain cases Ite gen- cally believed that the difference in potential is caused by the difference in the rate of diffusion ‘of oppositely charged ions. In the above exam>- ple, the charge acquited by a dilute solution is that of the faster moving ion (H*); chloride ions (CI-) diffuse much slower. The magnitude of the liquid junction potential may alfet the reversible potential positively or negatively depending on the mobilities of the ions. The most common method of removing liquid junction potential is toinsert aKCL salt bridge between the electrolytes, Porous barriers are also used, The introduc: tion of salt bridge minimizes the liquid junction potential. The KCI contained in the bridge, allows the migration of K* and Clr ions which carry most of the current and migrate with the same mobility ‘The potential of zinc is more negative, hence it is considered as an anode (Zn—> Zn** +20) and the potential of nickel is less negative than zine, hence itis considered as a cathode (Ni?*-} 2e—+ Ni). The sign of the potential ie changed for zinc as it oxidizes. From the potential obtained (40.51), itis clear that she reaction will proceed spontaneausly. 2.10 APPLICATION OF FREE ENERGY TO CORROSION CELLS Ik is known that corrosion reactions produce electrical energy. ‘The amount of work done by a cell is equal to the quantity of electri cal energy which it generates under constant pressure, temperature and concentration of the reaction, In an electrochemical reaction, electr- cal energy available is equal to the product of potential ofthe cell and the quantity of electrc- ity involved (volts x amperes x time). That is, Hlectrcal energy = Ex Q. This is equal tothe net work done by the cell. From Faraday’s law, Q is24 Principle of Corrosion Engincering and Corrosion Control for each gram equivalent of the reactants. For n gram equivalent ofthe reactants, is equal to nF. Work can only be performed if the free energy ofthe cell is decreased, a shown in Section 2.6.2 AG ake 0.44) where AG = change in Gibbs free energy of acelin joules per mole n= number of electrons involved inthe E Semfofthe cell in volts fall substances arcin their standard states (ie at nit activity) the expression (2.44) becomes: ae nFE" (245) Mlustrative Example 2.3 Forthecell[Cu/Cu"* (1. 0M)W/[Zn"* (1.0M)/Za, ra Mt for Zn? mr Solution ofthe Problem: A Giescson = ERAGE MAG) where i = products j= teactants ‘n= number of moles Gaon =2168.35-40~(—1475+40)] So, Since, Hence, =0.002V Fac Reaction does not take place simultancousl. 2.11 NERNST EQUATION ‘The Nernst equation expresses the emfofa eellin \erms of activities of products and reactants taking place in the cell reaction, Consider a general cell MAMITe Ma +Myt (2.46) ‘My and M; represent metal electrodes, such as ‘Cuand Zn, ina cell, andthe above reaction (2.46) «an be written as cutzttozntcu (247) ‘The free energy change (AG) of a reaction is given by the difference in the molar free energy fof products and reactantsas shown in Section 26. AG=EuAG() (248) By/AGU) ‘Therefore, the free energy change for the reaction (2.46) can be expressed as Bape + Gigs) (249) the substances aze in their standard states the above expression becomes AG =( (G+ Ge Set Gs) (250) Free energies of any metal, such a My at ste standard sate and any arbitrary state aze related through the following equation: Ga —Gy=RTIn my — (251) where ay, is the activity of metal Mi, is the universal gas constant, and equal to B31A4joules/degreelmole, and Tis absolutetemperature in degrees Kelvin, °K, which is (27.16+ °C), Subtracting equation (2.50) from eque- tion (2.49), we get Substituting from equation (2.51), we obtain: AG—AG’ =RT In ay, + RT In oy, = RT In ogg, RT In og ] es where the ‘a? values are any arbitrary activity values, for which AG is the corresponding free energy of that reaction, AG ie the free energy [ext ye AG-aG’=RTIn x | aay change for the reaction involving standard states As AG=—nKE, and also AG*=—nFE", from equations (244) and (2.45), respectively, the above equation (2.52) becomes: er Hu | (233) whence Suppose MM? B= Ein faitx 2af] =, “Daala] because mg and ae=1 Basic conceptsin corrosion 25 At2sc 0.059 z Fu=Ey tog [a] Equation (2.53) is a general form of the Nest equation, It expresses the emf involved in an clectrochemical reaction, such as equation (2.46) in terms of R, T, F, m activities of products and activities of reactants. However, the TUPAC sign convention requites the above minus sign to be replaced by a plus sign. The Nernst equation ig re-written to comply with the TUPAC sign convention, as RI oxidized state activities product TF Feduced sate activities product BoE Which is written regardless of which way round the redox reaction is written, Hence, for Zn=Zn"* +2e~, and for Za * +2e"=Zn, RT. BSB 4 Ein ty 2.11.1 APPLICATION OF NERNST EQUuaTION To A CORROSION REACTION A corrosion reaction can be considered as com- posed of two half cll reactions. One of the half cell reactions corresponds to ‘oxidation reaction taking place onthe ‘anode’ and the other half el reaction cartesponds to reduction reaction’ taking place on the ‘athodé of the cell The contribution of each half cell reaction tothe Nernst expression can be derived as follows: MoMftine @ 50) oxidation reaction at anode, and Myttne>M 0) (255) reduction reaction at cathode.26 Principles of Corrosion Engincering and Corrosion Control Equation (2.53) can also be re into expressions to comtespond to (@) and (ID ged actions (236) E* Standard potential, and E (258) (259) and (260) Equations (2.58) and (2.59) are Nernst equations forthe half ellreactions and equation (2.60) ethe [Nernst equation for the complete cell reaction, Equation (2.60) can be put into a mathematical form: activites of reactants in Mites ofrenctnis 9 nF activities of products 0 But, in addition to this statement (2.61), a sien convention is necessary as already mentioned and this wil be discussed in the next section, Since 03 x 8.314 x (273-425) 96500 =0.05915 at 25°C (2.62) 2,60) is more commonly used in the 0.05915 product of activities of reactants ® product of activites of product (2.63) ‘The expression (2.61) can also be written with the activities inverted, as, __RT,, product of activites of producte BaP 7p roduc ofactvilie ofreactants (264) But this equation is incomplete without « sign convention, Quite separate from the above considerations, standard Redox potentials are tabulated with reac tive metals like Za negative instead of positive, which accorde with the experimental fact that Za will actualy become negative because when Zn** ions leave it, then two electrons will appear in the ‘Zavmetal, to maintain a charge balance. Such’ reduction potentials are given in Table 2.1. By convention the cell reaction is writen as if the oxidation process is occurring at the electrode on the left and reduction on the right, This practice is in accordance with the International Union of Pure and Applied ‘Chemistry (TUPAC) Convention held in 1953 and modified in 1960. 2.12 SIGN CONVENTION ‘The older American Convention hae been to ‘use oxidation potentials rather than reduction potentials, The present practice is to use reduc tion potentials instead of oxidation potentials in accordance with the recommendation of TUPAC (International Union of Pure and Applied (Chemistry) and existing European practice ~ the general convention is thatthe cell eis given by The standard hydrogen electrode (SHE) is the reference point. The construction of hydrogenelectrode is shown in Fig. 2.10. By definition, SHE hhas zero potential at 25°C. It is assumed that oxi- dation occurs at the hydrogen electrode so that it is placed at the left-hand side of a cell dia- gram. Ifa cells composed of SIIE and some other electrode, then the measured voltage of the cells the electrode potential ofthe second electrode: Ee =Ex—0 Fea =Bx For example, ina galvaniccell made of hydrogen electrode anda zinc electrode (ZnvZn*' (1.0M)], the measured voltage is E= 0.763 volts Eig =—0.763V In the older textbooks, iyurogen electrode was placed on the right, and the cell potential becomes: Feat = Bat — Be The reaction was made oxidation and the sign was changed. Thus the electrode potential B5,..5 is +0.763 volts according to old convention. Fey =8iy~ (Ei) By =H078V Eo =E Evy = 0.763v0lts Which is opposite to that shown above. This should clarify the confusion caused in student's minds by different conventions, The simplest procedure avoids specifying ‘righ? and ‘lf? by just writing: RI, oxidized sate activites product tn ized stat activites product * ‘reduced state activities product which is written regardless of which way round the chemical equation is written. Basic concepts in corrosion 27 2.12.1 CELL EMF AND THE DIRECTION OF SPONTANEOUS REACTION ‘he followingisa step-by-step procedure to apply the above sign convention to a cell reaction in order to determine cell emf and direction of spontaneous reaction correctly. (1) Write the righthand clectrode reaction, ‘The rightchand electrode reaction is always reduction and the electron is always a reduc. ing agents Mite Ma ‘And reduction electrode potential is Ey (2) Write the left-hand electrode reaction. The Ieftchand electrode reaction is oxidation However, we write it az reduction reaction ‘because of the convention we are using! Mp+e- Me ‘And the reduction electrode potential is F. Subtract the leftchand electrode reaction and potential ftom those of right-hand clectrode to obtain cell reaction and cell potential: 8) Mj +M, =Ma+M} -E For example, calculate £° for the Daniel cel, From the table of reduction potentials, write the corresponding reactions =0337-(-0763V) 100V28 Principles of Corrosion Engincering and Corrosion Control Another example: Using a cell of Pb47Pb and Sa?/Sn, caleulate Ey Ee Few oR RoL ==0.126-(-0136) =o.0v M*+e5M, Zn Zn** 420 Cath 42e> Cu 2.12.2 POSITIVE AND NEGATIVE EMF A positive emf (E>0) signifies a deficiency of clectrons on the right-hand electrode because of the extraction of electrons from that electrode Therefore, the tendency of the right-hand lectrode is reduction (acceptance of electrons MgE-+e=Mg, if F>0). At the same time, positive emf signifies an excess of electrons om the lefthand electrode. Therefor, the electrode reaction is oxidation (My =M; +e) on that lec- trode, Thus, if B>0, the ell reaction has a tendency to proceed from lef o right: that i, electrons are produced by the lef-hand electrode and consumed by the right-hand electrode Iealso indicates that the eaction is spontaneous Conversely if <0, the reaction atthe ight- hand electrode is oxidation and the reaction at the letchand electrode reduction. The tendency of the reaction would, therefore, be to proceed from right to left andthe reaction would not be spontaneous igure 2.11 explainsthe flow ofclec- ‘rons inthe two situations explained above. The same convention can also be understood in tems offlow of postive current (postive chargedions) isto be noted that according tothe convention, ia cellis short cxeuted, and the positive current flows through the electrolyte from lft to sight, the emis positive. In this case the leftchand elec- lwode is the anode and the right-hand electrode e>0 >e) Figure 2.11 Implications ofthe sgn convention <0 (<8)Table2.2 Current flow conventions emf Currentilow Anode Cathode + LOR L R = RSL R L the eathode. Ifthe current flows from right to lef, the emf is negative. Table 2.2 summarizes the current flow convention ina cell From knowledge of cell potential it is thus possible to predict whether a reaction would pro- ceed spontaneously or not. From knowledge of potential of haf cells, and the eel potentials, it is possible wo predict whether a metals an anode or cathode or whether a corrosion reaction i likely to take place or not. An understanding of elec- trode potentil is of fundamental importance to the understanding of corrosion mechanism. Thie illustrated in typical probleme given below. lustrative Problem 2.4 Two half cell rections are given below: cutazescu, B=034(V) Yn? 42e=2 7p, E°=—0763(V) Their reduction potentials are given opposite to cach reaction, Calculate: (2) the emf ofthe cell and (b) show the spontaneous cell reaction Solution: In Fig, 22, the left-hand electrode (Zn) is the anode and the right-hand electrode (Cu) is the cathode according to the convention we studied earlier on. Therefore, zinc wll undergo oxidation and copper reduction as shown below. Hence: (9) Boy = Bj —By (acording to IUPAC convention) Ey Fey=+L100vats (®) Spontaneous cell reaction ie given by: cell reaction = cathodic reaction = anodic bona +c Basic concepts in corrosion 29 From the table of standard reduction poten- tials (Table 2.1), the reduction potential of Cu ig =0.34volts and that of Zn is -0.76 volt, The cm of the cell is positive, Hence the reduction is spontaneous and it should proceed from left to right. Ifthe position of the electrodes are nowinter- changed such that the copper electrode is placed fon the left and the zinc electrode on the right, the sign of the cell emf will change. Here, zine ectrode being on the right is treated as cathode and the copper on the left as anode according to the convention discussed easier in the chapter. “Therefore: Zn? 42e=Zn, = -0.7680 +2etCu, R= 4034 Subtracting anodic reaction from cathodic reac- tioa to obtain the cell reaction Zn? $CuRtZn+O\ ov The emf obtained is now negative which indi- cates that the reaction is not spontaneous and. the current ows from right to left. The left hhand electrode where the current originates is, therefore, the anode, and the right-hand elec- trode, the cathode. The polarity of the cell is, therefore, clearly established lustrative Problem 2.5 Calculate the reversible potential fora zine ele twode in contact with Za when the activity of sinc it dy,3+ = 10", Use TUPAC convention Solution We write the half el reaction Za 42eS Za, Ejy=—0.76V Apply Nernst equation: RT Eng =Eig+ Selo [ 726] 2953 sha] 0.764! z30. Principles of Corrosion Engincering and Corrosion Control Mlustrative Problem 2.6 Show that for the reduction reaction given below: 2Ht42e=H;, Ey =—0.0591pH Solution The reaction is 2H 42e=2Hz, Using Nems equation we obtain forthe above reaction: RI, [reactant Fant) =Eintaiy Ge! Tpreducte . oxidized state or Bani) Euston + Ge! Tredueed wate) ‘Changing to 2.303 log and substituting for R=8314I/(mol-K), F=964906, T=298°K, 2303RT/F =0.0591V. ‘The Nernst expression above can, therefore, be written a: Barong) = Bue +2059 LgK"] Now substituting pl expression we get: =—log(H*) in the above Exusany) = ~0.0591 pit Mlustrative Problem 2.7, Show that for the reaction: O;+22 (oH), Eyre) ~ Fone) ~9 991 sou Soluson The reaction s 03 +280.44¢°74(0H) (ina basic slution), and x £0 (eon-)* Note that Op is the oxidized state and OH is the reduced state, for the above reaction (from. TUPAC-Nernst expression) The activity (a) of an ion is defined by Lys where My = molality (mol/kg) of the ions in the solution, and a; is the activity coefficient. The activity coefficient a; for a given concentration can be found from a table af activ ity coeilicents given at the end of the chapter. In dilute solutions, the activity coefficients taken to be unity. If we take aq, =Po,/P°=1, when Po, Y= 1 bar, standard state and R=8.314 Jmol, F=96485C(g equiv)~!, T=298°K, and the term 2.303RT/F=0.0591, and substitute in the above expression, the oxygen electrode potential becomes: Eoouos) = Epon) 0.059108 on 1k can similarly be shown that in acid solu tion fora reaction, O2+2H,0+4e— 24,0, the ‘oxygen electrode potential becomes Rr oy tol (00) Sak on (at Substituting the values for the constants as above, we get Foy) =Bijoy +0.0592 log ays or since pH =—log ays, Boy “Koy ~ 005820 Mlustrative Problem 2.8 Calculate the potential of oxygen electrode at pH=140, Solutions ‘Onygen electrode reaction: in basic and neutral ‘environment is expressed as Or 42H:0+ 40+ 2420 Electrode potential equation for the electrode at 25°C is given by Hustrative Problem 2.7: Bo, =B3, —0.0592108 aon where og jou-)=—H4—log aan 14+pHt (Grom the knowledge of pH)Therefore, Ho, =F, —0.0592(-M4 +p) Substitute £5, =0.401 (from Table 2.1) Therefore, Eo, = 0.401414 0.0592—0.0592pH Fo, =0401-+0.828—0.0592pI1 and sot pH#=14, Fo, =0401-40828—0.828 and Fo, =0.401 Mlustrative Problem 2.9 In the cell reaction given below, what is the ratio of the activities of ionic species required to make the polarity reverse? Feb pSno Sn? + Fe Solution: Cell reaction: et Sno Sn Fe Rati of activities to make the polarity reverse at 25°C. Standard cell potential: o+tne Fig 0.441 ~(—0.140) sn The reaction in this case is non-spontaneous. Tat is, Fee electrode will act as ‘anode’ and Sn¥*/Sn electrode will acta ‘cathode; the reverse ‘ase of what was assumed in the problem, To reverse the polarity: (Overall cell potential i given by: Ty, mec Fey = Big t AE tect nf [aprodact) 230K, ae a Basic conceptsin corrosion 31 where: asp =H and ape= 1. 230387 a Req) =—03014 og 2 Keqi=0, Atthe turn of polarity. ‘Therefore, ogo 22280, ne as [aes ]_ 0.301 nF 0RF 25°C,n=2,T =298°K,R=8315 Jmol and F= 96500 C(gequiv.)* Then log Stet] = 0201296500 8 3058 314x 298 = 64107" at 25°C Arz0e&5x 104 Mlustrative Problem 2.10 ‘The emf of a cell made of Zn (anode) and 1 electrode (cathode) immersed in 0.7 M ZnCl i +0,690volts, What is the pH ofthe solution? Salton Given [2Zn**]=0.7M, For Zn** activity coetcient, 7 =06133 (Right) = 2+ +26" SH, (Left) > Zn?* | 2e7 Zn. B= -0782V Eco = Ee —E =H, ott) Hoe 0h. )] 0.0592 ~ {5x foskons]-loe[ec0-TI}32__ Principles of Corrosion Engincering and Corrosion Control 0.0582, Sap} +0762 0.11 volts 0.0592, Eau = 0.111 alts =log(0.82)] 2 Ilusteative Problem 2.12 Calculate the pressure of H required to stop corrosion of iron immersed in 0.1M FeCl, 0.0286{2pH] +0.762 +-0.0296(0.376) pHee = 0.0296{2pH]=0.762—0.650+0.011=0.083 | Seton (R92 4207 91h, 0.083 9 RPE Tagg PPR 28 (Wy +Be 427 Fe > plait R= +044 [oer ]=y x Fe] ‘Mustrative Problem 2.11 Calculate the theoretical tendency of nickel to cor- 0.10.75 rode in deserated water of pH1=8. Assume the ba =f hi corrosion products are H; and Ni(OH); and the Ea=Br—A, solubility product is 1.6107 Feat = Hig 0.0296[log(PH,)—log(a-)*] Solution ~ (Hf, -0.0296 log( re) —log(ay-))] Given: Ky =1.6 x 10-6, pl : Since, pH#=pOH=M—pOH=14=8=6 Given: plt=4=[am.]=10-4 6x10 Poco 8 7 =16x104 (0=0.44-00296 log(75 10°) pH] (sat e2e oat = PH a togi7.5x 10% ptt, (SNP 42° Ni Ta5g ~l°8"75*10"1eHs =(75x 105 pit, =7.32%10" 2 (logtptt, 210g (an) pH, = 97 « 10? atm 0.0592 z [logtasi) Ilustrative Problem 2.13 Calculate if silver would corrode when immersed in 05M CuCl to form solid AgCl. What is the tog (aes)] } corrosion tendency! . Solution > Fee) 0.02962 pH] +0.25 RR=0337V, you, =07 +-0.0296{ —log( 1.6% 10-9] Fijq=0220 =p Feet =—0.0296(2 8140.25 F doyst =0.47 x05=0233 +0.0296(4—I0g(1.6) =0ATx2x05=047() sou 426" cu (1) 2AgCl4 267 2Agt +201 0.0592 Feat Be, Eigr~ J [Mog( ace) Hoel agyr)] Hogi“)? ~logt ech] = Fea =0337-0.220~-0.0296[—logl y+) i =0.117—0.0296)0.632~2(~-0327)] = 2log( 4, =0.079%% Fog = 0.079valts 2.13 REFERENCE ELECTRODES 2.13.1 HYDROGEN ELECTRODE The hydrogen electrode is used asa reference for electrode potential measurements, Theoretically itis the most important electrode for use in aque- ‘us solutions. The reversible hydrogen electrode in a solution of hydrogen ions at exhibits 2 potential, which is assume: stall temperatures ‘The electrode consists of a platinum wire immersed in a solution (Fig. 2.10) containing hydrogen ions and saturated with hydrogen gas. Platinum is immersed completely in aqueous arsenic free hydrochloric acid, and hydrogen gee fice from oxygen and carbon monoxide is bub- bled to the platinum surface. Slowiy, the air is displaced by hydrogen and the reversible poten- ial ig achieved, Unfortunately, this electrode has some drawbacks. First, the reversibility of hydrogen clectrode cannot be maintained in oxidizing media. Second, if a current is wid woo- = = lero WO TO oro soo $970 FED EVO HISD GED ceLD OEE woo gee LTT 0tz0 B10 SLO EO FOLKD LHD IK S960 scl tet WT goo 2960 9620 OD SFO FOO FSD EGU 9960 oF of of oT so zo 10 «S00 «moo «0 soo 000 T1000 W (dayejout = ¥y) sorsjonrap2 Seons yo 03 yoo AMY ETALBasic concepts in corrosion 37 a0 0 wo +660 30 v0 ovo #0 wo sce 10 900 v7 so 900 wo ¥0 avo s60 #600 199 00 sso ‘sot Wo s100) <0 so zo sso tro sv0 ovo seo oro 9390 90 sro wo uso 0 1500 00 zo 90 s90'0 a0 60 «0 to $90 wr0 90 wo z0 a0 $690 390 wo wo 30 wo wo sv e200 70 S00 0 svo 390 soo ovo soo wo a wo seo oo #0 oreo ose 690 zo 990 390 0 svo evo sso s9r0 sro oso reo sco ozo «co 90 “0 wo vo wo evo ovo oc sco oro sco «co veo aro aro 950 3520 seo ovo sco wo ovo zo eo zo 3e0 we 90 Fo avo 0 0 sco wo v8 6e0 wo os 690 190 060 vice 060 160 +160 4050 os 20 380 a0 380 ovo 4050 vosuz souz ovuL, root ‘ONIL vad rom "6oN)a "paa POON rosen, SONEN TEN EN DN HN Fost rosin "paw font38 Principles of Corrosion Engincering and Corrosion Control Paste nusted | sm Bess Cable cal waersght {sees iiparmetces seman! Jortoaveen — eee SER = ‘to rubber bung: Coppertod J. — Pras case ogo. Excess CuSO. erie Figure 2.14 Reference copper-copper sulle electrode ‘The following i the conversion table for important reference electrodes (Table 2.4) Table24 Conversion able for important refer- cence electrodes Potential 9s Hydrogen Copper-copper _ Silver chloride (ev) sulfate (mV) (mV) 100 84 170 125 109 —203 450 134 —28 470 159 253, 500 =184 —78 525 =209 303, 550 234 320 375 259 333 00 284 —370 025 309 403 650 34 a8 of a wooo rus unclazes poveelin Saped aceon "atNod of mang contact) Conversion of Cu/Cu80, electrode potential into Ag/AgCl and hydrogen electrode potentials is expressed by the following equations: (a) emf (ys CusCuSO4) = emf (vs Ag/AgCl) — 50mV emf (vs Cu/CuS0,) 316mV © emf (vs H/T) ~ ‘The conversion table for reference electrodes is shown in Table 2.4 Mlustrative Problem 2.14 ‘Convert -0,900 V (on SCE, Sat.) to the SHE scale. Solution =0.900V (on SCE, Sat.)= Mlustrative Problem 2.15 Convert —0.916V (on SCE. 1.0N) to the SHE scale,Solution: ~0.916V (on SCE, LON) =-0916+0.280V (on SHE) = 0.636 (on SHE) Ilustrative Problem 2.16 ‘What is the potential on SHE scale, for an electrode which is at a potential of —0.920V. relative (o a AplAgCl reference in 0.01N KCL 325°C. Solutio: Cell reaction: AgCl+e—> Ag+CI" from equa- tion (2.63) Eqghing = 0.222 0.059 0g [a age = [y= [C7] =(0.901)(001) where ye = a0tivity coefficient for chloride ions ye =0.901 CI = concentration of chloride ions cr =001N age =9x 10 Exgsing = —0222—0.058]0g [9 10~ Fag ing =0.348V with respect to STI. Therefore, —0.820V (on AgiAgCl) = (—0.920-40.343)V (ith respect to SHE) lustrative Problem 2.17 The following reduction reactions ae given: (a) 0)421,0+4e=401- (b) O44 44e=21h0, Show that the single electrode potential for tach reaction at 25°C has the same potential dependence. Basic conceptsin corrosion 39 Solution: For reaction (2: ; toe Son + fet, Foxsott- —logaiy.-) 0.0591 0.401 log Po, 0.0592 108 a031- Replacing log doy-=pH—14 in the shove equation: ont- =0.401 0.0592 [pl 14] +0.03921o0gP9, 0.059 4 jon =1.23—0.0392pH14 Tog Po, For reaction (b) 0392 Foyaho=Foyno+ a [log Po, +o af] Boynnso =1.23 + 0.0582log ne + 2 tog Po, 00392 Eoyano=123~00592p HP Iog 2.14.5 EMF AND GALVANIC SERIES Table 2.1 gives the standard electrode potential of metals with reference to standard hydrogen, electrode (SHE) which is arbitrarily defined as 2e10. Potentials between metals are determined by taking the absolute difference between thei stan dard potentials, The determination of standard electrode potential is shown Fig, 2.15. Asshownabove, theclectrode potential oftwo lilferent metals in an electrode can be compared. Each metal in contact with an electrolyte of its fon forms a half cel. The most practical method of obtaining reliable and conaistent value of re tive electrode potential i to compare the value of cach half cell with a common reference electrode40 Principles of Corrosion Engincering and Corrosion Control Figure 2.15 Method of determination of standard slectrode potential “This common clectrode is the standard hyéro- gen electrode which consists of a platinum wire platinized by electrolysis surrounded by a solu- tion having a H! ion activity of (aps —1) of one and enveloped in a hydrogen gas at I atmosphere pressure, The potential ofthe hydrogen electrode is given by: Vv Ds PR(s) [Ha (Latm) [EE (ay The electrode potential of all metals is come pared with the standard hydrogen electrode and itis called the standard electrode potential (E") Between two metals, such az zine and ale rinum, aluminum is more active then zine [Ej.=—166V, F5, =—0.765V1. A metal with more negative potetil has a higher tendency #0 corrode (dissolve) thana metal withalessnegative Potential, although kinetic factors may intervene Ifthe potential of a metals less than hydeo- gen potetil, reduction rather than oxidation takes place (electrons are gained), MI-te—>M, “Metals which correspond to zlatively lower stan- dard potentials E° are called active metals and metals which corresponds to relatively higher sandard potential of lets negative potentials are called noble meta Cu, Ag, Au are examples of noble met als, whereas K, Li and Mg are between iron (Bj, = -0.443V) and zine (Bj, = -0.763V); ine is more active than iton.” Between copper (Fj, = +0.334V) and iver (+0.80V), Agismore noble than copper. If the electrode reactions ‘occurring on different metals at room tempera ture are arranged in accordance withthe value of standard potentials, an electrochemical series at 25°C is obtained (Table 2.1) 2.13.6 SUMMARY OF CHARACTERISTICS OF EMF SERIES (TABLE 2.1) (1) Metals with large positive potentials are called ‘noble’ metals because they do not dis- solve easly. Examplesare copper, silver, gold, «ee. The potential of noble metal is preceded bya positive (+) sign. ‘The electrode potentials are thermodynamic {quantities and have lite relevance to poten- tial of metals in solution encountered in @ ‘The em series lst only the electrode poten- tials of metals and not alloys. Alloys are not considered inthe emf series. (4) The emf series is based on pure metals. The more active metals, such as Na, Mg, Al, Zn are called ‘active metals’ Alloys are not considered in the emf series. From the reversible electrode potential in the standard emf series of metals, it is possi- ble to predict whether a particular metal will spontaneously dissolve. It gives an indication of how active the metal is but does not necessarily predict corrosion accurately for reason to be explained later in the next chapter. °) 6) @ a 2.13.7 APPLICATION OF EMF SERIES Following are useful applications of emt series: (1) A.tesselectropositive metal would displace 2 more clectropositive metal from one of its salts in aqueous solution. For instance, if a rod of zinc is placed in a solution of copper8) a sulfate, zine would dissolve in the solution and copper would be discharged: Zn Cu8O4 > Zn$04 + Cu Zn-+Za"* + 2e (oxidation) Cu**42e-+ Cu (reduction) Consequently, copper will deposit on the zine rod, Flectrode potentials indicate also the ten- dency of cations in aqueous solutions to be reduced ata cathode, For example, silver ions are reduced more readily than cupric ions, because silver is more electropositive ‘Metal ons above hydrogen are more readily reduced than the hydrogen ions with 100% efficiency ‘The metals in the series with high posi- tive potentials are recognized as metals with good comosion resistance. They show a litle tendency to pass from a metalic state to an ionic stale. Conversely, metals with high negative potentials show a tendency’ to corrode, but whether they corrode or not would depend on other factors also, For instance, iron has a potential of —0.440 V and indicates tendency to corrode, but if it develops a film of oxide it would not remain active, and hence, it would not corrode. This effect is used in formulating stainless steels, which are covered by an invisible oxide film, ‘The metal with a more negative potential is generally the anode, and the metal with, a les negative potential, the cathode. If zinc and aluminum are coupled, aluminum ‘would become the anode (Ej; =—1.67V) and zinc (Ej,=~0.763V) the cathode. It may be expected that in the presence of metals Which are mote negative than hydrogen in the emf series, hydrogen reduction would be the preferred process. That is, however, not always the cage, Metals as negative as zine (B, =—0.768V) can be plated from an acid solution without kberation of hydrogen. In the case of aluminum, however, hydrogen evolution would be the preferred process, ang, therefore, aluminum is deposited by clectrolysis of a non-aqueous melt in order not to give any chance for the liberation of Basic concepts in corrosion 41 hydrogen which may enter the metal and ‘cause its embrittlement, The emf series is also utefl for the electrolytic refining of the metals 2.13.8 LIMITATIONS OF EMF SERIES ‘The following are the obvious limitations of the EME series: (1) The emf series lists only pure metals which have only a limited use in engineering appli- ‘ations. Alloys are of major interest to ‘engineers rather than pure metal. ) The electrode potential has litle relevance to potentials of metalsin solutions, in which the potential of interes isthe corrosion potential nd not the electrode potential ofthe metal. ‘The position of metals in the emf series is determined by the equilibrium potential of the metal with the concentration of ions at unit activity. Prediction about galvanic cou- pling can only be made when the two metale {forming the galvanic couple have ther ionic activities at unity. Ifthe above conditions are not met, accurate prediction af galvanic con- version by emf series would not be possible. ‘The activity of ions in equilibrium with 4 given metal vary with environment and, therefore, accurate predictions of galvanic not generally possible. ‘The em series predicts the tendency to cor rode but it cannot predict whether corrosion, would actualy take place. For instance, on the basis of some negative potential, iron shows tendency to corrode, however, if it develops a passive film in some environment it would not corrode, ‘The emf series cannot alveays predict the effect of environment, For instance, in food ‘ans, the polarity of tin may be critical. The potential of ron (F;, = ~0.44) is more nega- tive than the potential of tin (E3, = 0.1369). However, inthe presence of certain type of foods in food cans, tin can become active to iron, Such a change cannot be predicted by emf series, 0°) @ 6)42. Principles of Corrosion Engincering and Corrosion Control "The effect of lm formation on the tendency ‘of the metal to passivate solution cannot be predicted by emf series, For instance, ttae ‘nium and aluminum are more negative than, iron, However, in certain environments they form a film which makes their potential less active than iron. The effect of film forma tion on the tendency ofthe metals to corrode is kinetic and cannot be predicted by the thermadynamic emf series. 2.13.9 IR DROP (OHMIC Drop) ‘The IR drop isthe ohmic voltage that results from. the electric current flow in ionic electrolytes, such as dilute acids, salt water, etc. When the refer- tence electrode for measurement of potential i placed inthe electrolyte, an electrolytic resistance exists along the line between the test and the refer- cence electrode, Because the current flows through. an electrolyte resistance an ohmic voltage drop is also automatically included in the measurement of potential z Fast ~ Erfeence IR drop (ohmic drop) is an unwanted quality which must be eliminated to obtain an accurate potential measurement. By Ohm's Law, E = IR The IR drop in a flash light battery, for instance, contribute to the internal resistance For any measurement, the reference electrode is placed closed to the working electrode, if this fs not done the measurement would be inac- curate as it would include an IR drop. This is because the potential whieh is measured will always include the potential difference across the clectolyte which ir between the reference and. working electrode. A+ E is measured ar IR, the potential ie called IR drop. The IR contribution ‘mist be subtracted to obtain the current emf of the cell. 2.13.9.1 Methods to Remove IR Drop a. Extrapolation Method The emf is measured with the reference dlec- trode placed as close to the working electrode as ~. ance (m) Figure 2.16. Extrapolation method possible in the electrolyte. The electrode is moved at definite intervals of distance and potential (F}is measured, Emfis plotted asa function of distance and the curve is extrapolated to zero distance: Fig 2.16. This method is applicable in electrolytes of high resistance, such as soils, b. Current Interruption Method When there eno current flaw there cannot be any IR drop. Hovrever, when a current is flowing IR aga. Curves identified as 0, ~2, ~4, —6 cor- sesponds 0 10°, 107%, 10-4, 10°, respectively (Fig. 219), 2.14.4 REGIONS OF IMMUNITY, CORROSION AND PASSIVITY IN PoURBAIX DIAGRAMS Figure 2.20 shows the regions of immunity, corrosion and passivity which are described below. 2.14.4.1 Immunity Region. “The region of immunity shown in the Pourbsix diagram! Oindicate that corrosion can- not occur in this region. For instance, at a point Xin the diagram asthe activity of Fe would be verylow (~10-®),xsHe) os Figure 219 Simpliicd Pourbaix diagram for ron/water system Basic concepts in corrosion 4950 SHE ‘CORROSION. Figure220_ Pourbuix diagram forthe iron-water system, 2.14.42 Corrosion Region As iron is twansformed to soluble species, it is expected that iron would corrode. 2.14.43. Region of Passivation An oxide species in contact with an aqueous sole tion along a boundary would not allow corrosion to proceed if it i impervious and highly adher- ent The thin layer of oxide on the metal surface, such as Fes» oF Fes, is highly protective under the above condition, Metals like aluminum and steel are known to resist corrosion because of development of oxide films in the ar. 2.14.5 SOME EXAMPLES OF POURBAIX DIAGRAMS. 2.14.5.1 Pourbaix Diagram for Aluminum A Pourbaix diagram for aluminum and H:0 system is shown in Fig. 2.21. The pH varies Principles of Corrosion Engineering and Corrosion Control PASSIVITY pa 25°C showing nominal zones of immunity (axis) from acidic at low pHf to caustic at high pH. Line a is the hydrogen line below ‘which water is no longer stable and decomposes {nto hydrogen and OH" (alkaization). Line bis the oxygen line above which water decomposes into hydrogen, oxygen and 11 (acidification) Water is stable between regions (a) and (b). In acidic conditions Al dissolves as AI? In alkaline conditions aluminum dissolves as AIO, ALOs | O»2A105 1 2H In neutral solutions (4-8 pH), the hydroxide is insoluble which makes aluminum surface passive ‘Aluminum dissolves both in acids and bases. 2.14,5.2 Pourbaix Diagram for Copper ‘A Pourbaix diagram for copper/water system is shown in Fig. 2.22. Copper (B° ~ 0.337V) is ‘more noble than iron (Ej, =—0.444V), however, it is more stable in water (SHE) than iron Gopper is nat passive in acid electrolytes. The oxide of copper, Cu* and Cu’ are onlyBasic conceptsin corrosion 51 -~ Loo Le ew a ap, 7 > ~ a Ao ama Disschiton | Passivation Dissolaion a Figure 2.21 Pourbaix dag Figure 222 Pourbsix diagram forthe copper-water system at 25°C forthe sluminum-orater syetern 325 pH protective in weakly acidic and alkaline elec- {rolytes. The region of immunity extends above the line (a) in the diagram which represents oxj- gen evolution, Ifthe potential of copper is made ‘more noble, it would corrode under mildly acidic and strongly acidic conditions. It would also cor- rode under strongly alkaline conditions in higher oxidizing potentials, ‘The scope of the chapter does not permit a broader treatment of Pourbaix diagrams, By den- ‘ifying the pH and potential ranges, itis possible to control the corrosion of metals in aqueous environment, Aluminum is highly active but it can be used with a minimum risk of corrosion because ofits tendency to form protective oxide films which prevent the metal from corrosion, Although titanium is highly active with a very narrow immunity zone towards the bottom of the diagram, ithas an excellent tendency for pas- sivation as shown by a highly extended passive zone which extends over the entire range of pH. Titanium, however, corrodes under reducing and highly oxidizing conditions ae shown inthe lower left region of the pli-potential diagram,52. Principle of Corrosion Engincering and Corrosion Control 2.14.6 BENEFITS OF POURBAIX DiAcRams Pourbaix diagrams offer a large volume of thet= modynamic information in a very efficent and compact format. The information inthe diagrams can be beneficially used to control corrosion of pure metals in the aqueous environment. By slkering the plI and potential to the regions of immunity and passivation, corrosion ean be controlled, For example, on increasing the pil of environment in moving to slightly alkaline regions, the cortosion of iron can be controlled. ‘This can be achieved by water treatment, Sim- ilarly, changing the potential of ion to more negative values eliminate corrosion, this tech- nique is called cathodic protection, Alto, raising the potentials to more positive values reduces the corrosion by formation of stable films of oxides fon the surface of transition metals. Stel in rein- forced concrete does not corrode if an alkaline environment is maintained. On the contrary, an alkaline environment for aluminum is a disaster if the pH exceeds 80. The above example ceazly demonstrate the merits of Pourbaix diagrams in prediction and conteol of corrosion. However, there are several limitations of these diagrams, Which are summarized belove 1. These diagrams are purely based on thermo- dynamic data and do not provide any infor mation on the reactions. The thermodynamic stability may not be achieved tothe kinetics ofthe reaction, No information is provided in the rates of reaction, 2. Consideration is given only to equiibrivm conditions in specified environment snd fac- tors, such ab temperature and velocity are not considered which may seriously affect the 3, The activity of species is arbitrarily selected as 0-F pmol which is not realistic 4, Pourbsix diagrams deal with pure metals which ate not of much interest tothe engi- 5, Allinsoluble products are assumed to be ps tective which isnot trae, as porosity, thickness, and adherence to substrate ae important fac. tors, which contral the protective ability of insoluble corosion products Although the above disadvantages appear to be substantial, the advantages offered by the Pourbaix diagrams far outweigh their limitations QUESTIONS A. MULTIPLE CHOICE Questions Select one best answer: 1, The electrode potential ofa metal is | The potential which exist atthe inter- face between the metal and the elec- trolyte J The potential between the anodic and cathodic areas of the metal |] The potential between two m« immersed completely in the same elec- ] The potential of a metal with respect to another metal, which is at a higher 2, The double layer ie formed as a result of| | tractive forces between negative charged metal surface and positive fons only | repulsive forces between like positive ions only, J both attactive and repulsive forces between ions | None of the above 3, The most acceptable method of obtaining standard electrode potential is by | comparing the electrode potentials of ‘metal half ell with a hydrogen half cell, | comparing the electrode potential of a metal immersed in a solution ofits ions atany concentration, with thebydrogen half cell[| comparing the electrode potential of ‘metal with any standard electrode, such as Ag-AgCl or Calomel electrode | None of the above A galvanic cell is formed [1 when two metals are immersed in solu tions differing in concentration [1 when two different metalsareimmersed in one electrolyte [1 when two different metals are exposed toair [J when two metals are brought close together and electrically insulated from ‘one another In concentration ells [| the metal is in contact with two half cell having the same electrolyte but at different concentrations [1 the metal is in contact with two half ‘els, having the same electrolyves with the same concentration [| no liquid junction i present [| there is no migration of fons from one electrolyte to another electrolyte If the free energy of a reversible process is negative, itimplies that [| the cell reaction is spontaneous [| the cell reaction isnot spontaneous [| the cell reaction proceeds from right tolef [1 no reaction takes place at all The value of 2.303R7)/Fat 25°C varies with [1 temperature [| the metal being considered [| the melting temperature of the metal [| None of the above IEE > 0, the cell reaction [| proceeds in forward dizection [| proceeds in reverse direction Basic conceptsin corrosion 33 [1] does not proceed [1] None ofthe above 9, The most common electrodes used for mea- f corrosion potentials are: (Mark two correct answers) 10. A galvanic series is [1 a list of alloys arranged according to their corrosion potentials in @ given environment a list of metals and alloys according to their corrosion potentials in a given environment alist of standard electrode potentials of alloys or metals arranged in order of their values a grouping of metals and alloysbased on their ability to get oxidized in a stated environment B. REVIEW QUESTIONS 1, Distinguish between: 2) Metalic conduction and electrolytic con- duction, ) Standard electrode potential and sion potential, ©) Anode and cathode. 4d) Flectronic conduction and ionic conduc tion, 2, In the sign convention adopted by IUPAC: 4) What does the right-hand electrode indi- cate? ) What does the leftchand electrode indi- cate? ©) How the cell potential, Eis obtained? 4) What does the positive sign of the cell indicate?